Triphenylsilane-fused Porphyrins

Kenichi Kato; Jun Oh Kim; Hideki Yorimitsu; Dongho Kim; Atsuhiro Osuka

doi:10.1002/asia.201600424

Triphenylsilane-fused Porphyrins

Chem Asian J. 2016 Jun 6;11(11):1738-46. doi: 10.1002/asia.201600424. Epub 2016 May 9.

Authors

Kenichi Kato¹, Jun Oh Kim², Hideki Yorimitsu³, Dongho Kim⁴, Atsuhiro Osuka⁵

Affiliations

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
² Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
³ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. yori@kuchem.kyoto-u.ac.jp.
⁴ Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea. dongho@yonsei.ac.kr.
⁵ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan. osuka@kuchem.kyoto-u.ac.jp.

PMID: 27124659
DOI: 10.1002/asia.201600424

Abstract

A reaction sequence of 2-(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila-Friedel-Crafts reaction has been explored for the synthesis of mono-triphenylsilane-fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis-triphenylsilane-fused porphyrins 7 M and 8 Ni. A triply linked triphenylsilane-fused Ni(II) porphyrin, 13 Ni, was synthesized in a stepwise manner involving the above reaction sequence and a final Pd-catalyzed C-H activating arylative cyclization. The silicon atom in 13 Ni takes a distorted planarized structure with an almost perpendicular Si-phenyl group, causing an electronic effect due to effective σ*-π* interaction.

Keywords: electrophilic substitution; fused-ring systems; porphyrinoids; sila-Friedel-Crafts reaction; silicon.

Publication types

Research Support, Non-U.S. Gov't